Beta-hydroxyalkylated hydrazone dyestuffs

ABSTRACT

HYDRAZONE DYESTUFFS OF THE FORMULA   ((-X-N(+)(-R1)=)&gt;C-CH=N-N(-CH(-R2)-CH(-R3)-OH)-)M-B   M(AN(-))   WHEREIN R1 DENOTES ALKYL, ARALKYL, ARYL, CYCLOALKYL OR A RADICAL OF THE FORMULA   -CH(-R4)-CH(-R5)-OH   R2 AND R3 DENOTE HYDROGEN, ALKYL OR ALKENYL, R4 AND R5 DENOTE HYDROGEN, ALKYL, ALKENYL, ALKINYL, ARYL, ARALKYL OR CARBOXYL, X DENOTES THE RESIDUAL CONSTITUENT OF A 5-MEMBERED OR 6-MEMBERED HETEROCYCLIC RING, B DENOTES AN AROMATIC OR HETEROCYCLIC RADICAL, M DENOTES THE NUMBERS 1 OR 2 AND AN(-) DENOTES AN ANION, ARE VALUBLE FOR DYEING AND PRINTING OF NATURAL AND SYNTHETIC MATERIALS.

United Pew Y 31,812,107 ,B-"HYDROXYALKYLATED HYDRAZONE DYESTUFFS Gunther Boehmke, Leyerkusen-Grossendriesch, and Ernst Schmitt, Cologne, Germany, assignors to Bayer Aktiengesellschaft, Leverlrusen, Germany I No Drawing. Filed May 2, 1972, Ser. No. 249,649 Claims priority," application Germany, May 4, 1971, P 21 22 038.2

Int. Cl. C09b 23/00 US. Cl. 260-240 G 13 Claims ABSTRACT OF THE DISCLOSURE "Hydrazone dyestufls of the formula CCH- -I -I=N B (ill- R2 (IE-R3 wherein R denotes alkyl, aralkyl, aryl, cycloalkyl or a m An radical of the formula -oH-R,

R and R denote hydrogen, alkyl or alkenyl, "R and R denote hydrogen, alkyl, alkenyl, alkinyl; aryl,- aralkyl or carboxyl, X denotes the residual constituent of a S-membered or 6-membered heterocyclic ring, Edenotes an arcmatic or heterocyclic radicaLm denotes the numbers 1 or 2 and An denotes an anion, are valuble for dyeing and printing of natural and synthetic materials.

The subject of the invention are hydrazone dyestuffs of the formula i wherein R denotes alkyl, aralkyl, aryl, cycloalkyl or a radical of the formula -CHR4 H-Rs The invention also relates to mixtures of these hydrazone dyestuffs. A further subject of the invention are processes for the manufacture of these dyestuffs and their 3,812,107 Patented May 21,, 1974 ice a use for dyeing and printing natural and synthetic materials, as well as the materials dyed and printed with these dyestuffs.

Non-ionic substituents are, for example, alkyl radicals such as methyl, ethyl, n-propyl, 'n-butyl, n-pentyl, isopropyl, isobutyl, tert.-butyl, pentyl, n-hexyl, 2-ethylhexyl, n-octyl, octyl, n-nonyl, nonyl, n-decyl, decyl, n-dodecyl, dodecyl, n-octadecyl and n-hexadecyl, alkenyl radicals such as vinyl, allyl, methallyl, crotyl, hexen-(Z-yl, and 2- ethy1hexen-(2)-yl, alkinyl such as ethinyl, and propargyl, cycloalkyl radicals such as cyclohexyl and Z-methylcyclohexyl, aryl radicals such as phenyl, p-chlorophenyl and pmethoxyphenyl, aralkyl radicals such as benzyl, 4-methylbenzyl, 4-methoxybenzy1 and phenethyl, aralkenyl radicals such as styryl, alkoxy radicals such as methoxy, ethoxy, n-propxy, n-butoxy, n-hexyloxy, n-octyloxy, n-decyloxy and n-dodecyloxy, alkenoxy radicals such as allyloxy, methallyloxy and crotyloxy, alkinoxy radicals such as propargyloxy, aryloxy radicals such. as phenoxy, 2-methylphenoxy, S-methylphenoxy, 4-methylphenoxy, 2-chlorophenoxy, 3-chlorophenoxy, 4-chlorophenoxy, 4-nitrophenylphenoxy, 4-methoxyphenoxy, 4-ethoxyphenoxy and 4- methylmercaptophenoxy, carboalkoxy radicals such as carbomethoxy, acyloxy radicals such as acetoxy, alkylmercapto radicals such as methylmercapto and ethylmercapto, arylmercapto radicals such as phenylmercapto and 4-methylphenylmercapto, alkylsulphonyl radicals such as ethylsulphonyl, aminosulphonyl radicals such as dimethylaminosulphonyl, arylamino radicals such as phenylarnine, acylamino radicals such as acetylarnino, alkylsulphonylamino radicals such as ethylsulphonylamino and also halogen such as fluorine, chlorine and bromine and nitrile, cyanato, isocyanato, nitro, hydroxyl and mercapto.

Suitable alkyl radicals are, for example, the methyl, ethyl, n-propyl or n-butyl radical and their derivatives which are substituted by the abovementioned radicals, such as chloromethyl, trifiuoromethyl, ,8-chloroethyl, )3- mcthoxyethyl ,8-cyanoethyl and fl-hydroxyethyl.

Suitable alkenyl radicals are, for example, the allyl,

methallyl or crotyl radical and their derivatives which are substituted by the abovementioned radicals, such as ychloroallyl.

Suitable alkinyl radicals are, for example, the propargyl or butin-(2)-yl-(1) radical.

Possible anionic radicals Anare the organic and inorganic anions which are customary for cationic dyestuffs.

Inorganic anions are, for example, fluoride, chloride,

bromide and iodide, perchlorate, hydroxyl, radicals of S containing acids, such as bisulphate, sulphate, disulphate' and aminosulphate; radicals of nitrogen-oxygen acids, such as nitrate; radicals of oxygen acids of phosphorus, such as dihydrogenphosphate, hydrogenphosphate, phosphate and metaphosphate; radicals of carbonic acids such as bicarbonate and carbonate; further anions of oxygen-acids and complex acids, such as methosulphate, ethosulphate,

hexafiuorosilicate, cyanate, thiocyanate, ferrocyanide,

ferricyanide, trichlorozincate and tetrachlorozincate, tribromozincate and tetrabromozincate, stannate, borate, di-

vanadate, tetravanadate, molybdate, tungstate, chromate, bichromate and tetrafluoroborate, :as well as anions 0f esters of boric acid, such as of the glycerine ester of boric acid and of esters of phosphoric acid, such as of methyl 3 propionic acid, 3-chloropropionic acid, 2-chlorobutyric acid, 2 hydroxypropionic acid, 3-hydroxypropionic acid, O-ethyl-glycollic acid, thioglycollic acid, glyceric acid, malic acid, dodecyltetraethyleneglycol-ether-propionic acid, 3-(nonyloxy)-propionic acid, 3-(isotridecyloxy)- propionic acid, 3-(isotridecyloxy)-diethyleneglycol-ethcrpropionic acid, the ether-propionic acid from the mixture of alcohols with 6 to 10 carbon atoms, thioacetic acid, 6-benzoylamino-2-chlorocaproic acid, nonylphenoltetraethyleneglycol-ether-propionic acid, nonylphenoldiethyleneglycol-ether-propionic acid, dodecyltetraethyleneglycolether-propionic acid, phenoxyacetic acid, nonylphenoxyacetic acid, n-valeric acid, ivaleric acid, 2,2,2-trimethylacetic acid, n-caproic acid, Z-ethyl-n-caproic acid, stearic acid, oleic acid, ricinoleic acid, palmitic acid, n-pelargonic acid, lauric acid, a mixture of aliphatic carboxylic acids with 9 to 11 carbon atoms (Versatic acid 911 of Messrs. Shell), a mixture of aliphatic carboxylic acids with 15 to 19 carbon atoms (Versatic acid 1519 of Messrs. Shell), coconut fatty acid first runnings, undecanecarboxylic acid, n-tridecanecarboxylic acid and a coconut fatty acid mixture; acrylic acid, methacrylic acid, crotonic acid, propargylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, iminoacetic acid, nitrilosulphonic acid, methanesulphonic the isomer mixture of 2,2,4- and 2,4,4-trimethyladipic acid, sebacic acid, isosebacic acid (isomer mixture), tartaric acid, citric acid, glyoxylic acid, dimethyl-ether-a,u'-dicarboxylic acid, methylene-bis-thioglycollic acid, dimethylsulphide-a,u-dicarboxylic acid, 2,2'-dithio-di-n-propionic acid, fumaric acid, maleic acid, itaconic acid, ethylene-bisiminoacetic acid, nitrilosulphonic acid, methanesulphonic acid, ethanesulphonic acid, chloromethanesulphonic acid, 2-chloroethanesulphonic acid and 2-hydroxyethanesulphonic acid, and mersolate, that is to say C -C parafiinsulphonic acid obtained by chlorosulphonation of paraflin oil.

Suitable radicals of cycloaliphatic carboxylic acids are, i

for example, the radicals of cyclohexanecarboxylic acid and cyclohexene-3-carboxylic acid and radicals of araliphatic monocarboxylic acids are, for example, radicals of phenylacetic acid, 4-methylphenylacetic acid and mandelic acid.

Suitable anions of aromatic carboxylic acids are, for example, the radicals of benzoic acid, Z-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 4-tert.- butylbenzoic acid, 2-bromobenzoic acid, 2-ch1orobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, 2- chloro-4-nitrobenzoic acid, 6-chloro-3-nitrobenzoic acid, 2,4-dinitrobenzoic acid, 3,4-dinitrobenzoic acid, 3,5-dinitrobenzoic acid, Z-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, Z-mercaptobenzoic acid, 4- nitro-3-methylbenzoic acid, 4-aminobenzoic acid, S-nitro- Z-hydroxybenzoic acid, 3-nitro-2-hydroxybenzoic acid, 4- methoxybenzoic acid, 3-nitro-4-methoxybenzoic acid, 4- chloro-3-hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, chloro 2 hydroxy-3-methylbenzoic acid, 4- ethylmercapto-Z-chlorobenzoic acid, 2-hydroxy-3-methylbenzoic acid, 6-hydroxy-3-methylbenzoic acid, 2-hydroxy- 4-methylbeuzoic acid, 6-hydroxy-2,4'dimethy1benzoic acid, 6-hydroxy-3-tert.-butylbenzoic acid, phthalic acid, tetrachlorophthalic acid, 4-hydroxyphthalic acid, 4-methoxyphthalic acid, isophthalic acid, 4-chloroisophthalic acid, 5 nitro-isophthalic acid, terephthalic acid, nitroterephthalic acid and diphenyl-3,4-carboxylic acid, o-vanillic acid, 3- sulphobenzoic acid, benzene-1,2,4,5-tetracarboxylic acid, naphthalene 1,4,5,8 tetracarboxylic acid, biphenyl-4- carboxylic acid, abietic acid, phthalic acid mono-n-butyl ester, terephthalic acid monomethyl ester, 3-hydr0xy-5,6, 7,8 tetrahydronaphthalene 2 carboxylic acid, 2-hydroxy l-naphthoic acid and anth aq Y acid.

Suitable radicals of heterocyclic carboxylic acids are, for example, the radicals of pyromucic-acid, dehydromucicacid and indolyl-3-acetic acid.

Suitable anions of aromatic sulphonic acids are, for example, the radicals of benzenesulphonic acid, benzene- 1,3-disulphonic acid, 4-chlorobenzenesulphonic acid, 3- nitrobenzenesulphonic acid, I 6-chloro-3-nitrobenzenesulphonic acid, toluene 4 sulphonic acid, toluene- 2-sulphonic acid, toluene-w-sulphonic acid, 2-ch1orotol uene-4-sulphonicacid, l-hydroxybenzenesulphonic acid, n-dodecylbenzenesulphonic acid, 1,2,3,4 tetrahydronaphthalene-6-sulphonic acid, naphthalene-l-sulphonic acid, naphthalene-1,4disulphonic acid or naphthalene-1,5- disulphonic acid, naphthalene-1,3,5-trisulphonic acid, 1- naphthol 2 sulphonic acid, 5-nitronaphthalene-2-sulphonic acid, 8 aminonaphthalene-l-sulphonic acid, stilbene-2,2'-disulphonic acid and biphenyl-2-sulphonic acid.

A suitable anion of heterocyclic sulphonic acids is, for example, the radical of quinoline-S-sulphonic acid.

Further possibilities are the radicals of arylsulphinic, arylphosphonic and arylphosphonous acids, such as benzenesulphinic and benzenephosphonic acid.

Colorless or colorless almost anions are preferred. Preferred anions for dyeing from aqueous solution are those which do not excessively impair the solubility of the dyestuffs in water, For dyeing from organic solvents, preferred anions are frequently also those which assist or at least do not adversely influence the solubility of the dyestufi in organic solvents; examples are the anion of tetrapropylenebenzenesulphonic acid, n-dodecylbenzenesulphonic acid, n-tetradecanecarboxylic acid and ethylhexylcarboxylic acid.

'A preferred group within the dyestuffs according to the invention are those of the general formula I l cum-on, a), tumm -0H,

R11 rec pe 1|"a H-Rq I H4 I H (II) wherein I p R denotes C to C -a'lkyl, phenyl, benzyl, phenethyl or a to C -alkinyl, pheny1, benzyl, C to C -alkoxymethyl,

C to Cg-alkenyloxymethyl, allyloxymethyl or phenoxymethyl, v

R denotes hydrogen, C to C -alkyl, C or C -alken'yl,

C to .C -alkinyl, phenyl, benzyl, C to C -alkoxymethyl, C to C -alkenyloxymethyl, phenoxymethyl or allyloxymethyl, with at least one of the radicals R or R being hydrogen or C to C -alkyl, R denotes hydrogen or one or more radicals such as halogen, nitrile, nitro, C to C -alkyl, phenyl, benzyl, C to G -cycloalikyl, C to C -alkoxy, phenoxy, benzyloxy, amino, C to C dialkylamino, sulphamoyl, C to C -alkylmercapto, C to C -alkylsu1phonyl, phenylsulphonyl, benzylsulphonyl, carboxyl, C to C -alkoxycarbonyl, carboxy-C; to C4-alky1, phthalimido-C; or C -alkyl or the ..radica1.of a'fused S-membered or 6-membered carbocyclic or heterocyclic ring,'- 1 I 1 Y I a denotes the numbers 0, 1 or 2,

b denotes the numbers 0, 1 or 2, '13 denotes an aryl' radical which can be fused to 5- membered or 6-membered hetero rings and An denotes an anion and i the alkyl, alkenyl, alkinyl, aralkyl, aryl, cycloalkyl and heterocyclic radicals can be substituted by non-ionic substituents. I

Particularly preferred dyestuflfs are thoseof the general formula.

wherein v v I V I v I R denotes methyl, ethyl, n'-propyl, isopropyl or n-butyl, octadecyl, phenyl, benzyl, p-nitrobenzyl, phene thyl or p-nitrophenethyl or a radical of the'tormula I methylsulphonyl, ,ethylsulphonyl, phenyl, p-nitrophenyl,

.- 'benzyl, 4-methoxybenzyl, 'cyclohexyl, cyclopentyl, trifluoromethyl, trichloromethyl, carboxy, carboxymethyl, 1, carboxyethyl, carbomethoxy, carboethoxy, phthalimidomethyl or the residual part of a fused carbocyclic 6- membered ring which can in turnbe substituted by chlorine, bromine, nitrile, nitro, methyl or methoxy, R denotes hydrogen, methyl, ethyl, n-propyl, isopropyl, nn-butyl, n-pentyl, isobutyl, n-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl isodecyl, n-dodecyl, n-hexadecyl, 'n-octadecyl; chloromethyl, fl-chloroethyl, vinyl, allyl, ethinyl, propargyl, phenyl, benzyl, methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, isobutoxymethyl, n-hexyloxymethyl, n-octyloxymethyl, n-decyloxymethyl, n-nonyloxymethyl, n dodecyloxymethyl, allyloxymethyl, methallyloxymethyl, crotyloxymethyl, 'methyl, phenoxymethyl or 4-methoxyphenoxymethyl, R denotes hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butylQn-pentyl, isobutyl, n-hexyl, isohexyl, n-octyl, I isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, n-hexadecyl, n-octadecyl, chloro methyl, flehlorpethyl, vinyl, allyl, ethinyl, propargyl, phenyl, be'rizyl, inethoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, isobutoxymethyl, n-hexyloxymethyl, n-octyloxymethyl, n-decyloxymethyl, n-nonyloxymethyl, n dodecyloxymethyl, allyloxymethyl, methallyloxymethyl, crotyloxymethyl, propargyloxymethyl, phenoxymethyl or 4-methoxyphenoxymethyl, with at least one of the radicals R or R being hydrogen, methyl or ethyl, e B denotes an aryl'radical whichcan be substituted by "5- 'memberedon 6-m'embered hetero rings, with nonionic propargyloxyt substituents being optionally present in i Am? denotes; an anion.

Amongst these compounds, the dyestuffs of the formulae IV, V and VI should be singled out:

CH3 w R21 CHa 3 R22 Q l (EH-R10 I ra 1 -Rzo w H (IV) wherein R denotes methyl or ethyl, R denotes hydrogen, methyl or ethyl, R denotes hydrogen, methyl or ethyl, Y R denotes hydrogen, chlorine, methyl, methoriy, ethoxy,

benzyloxy, carboxy, carbomethoxy or carboethoxy, R denotes hydrogen or one or more radicals such-as methyl, methoxy, ethoxy, i-propo xy, benzyl or together with the phenyl ring denotes a naphthyl, carbazolyl or diphenylene oxide radical and An denotes an anion;

R21- C s Rn CH-RIB l CH-Rrn -Rzo OH OH (V) wherein the radicals R to R and An have the meaning indicated in the formula IV, and

I CH3 Rn rCHa OH= -N Q JJH RQ, H-RI, v v

I,H"'R24 H-Rgug i OH H (VI) wherein the radicals R to R and An have the meaning indicated in the formula IV and i 1 i v R denotes hydrogen, methyl, ethyl or ally oxymethyl and R ;den0tes hydrogen, methyl ethyl, and allyloxymethyl.

A further preferred group within the dyestuifs I according to the invention are those of the general formula N N i1 1 a "i Moran-mist I Ant-i 27 H ,HR v

H -Ra g H f .kvin w e 1 I a r .1 R denotes methyl, ethyl, n propyl, n-butyl, cyclohexyl,

' 'phenyl,-"p-chlorophenyl or p-methylphenyl,

R denotes niethyl,'ethyl,' n-propyl, n-butyl, cyclohexyl, phenyl', p-chlorophenyl or p-methylphenyl, 4 R 5 denot'eshydrogen, methyl, phenyl, p-chlorophen'ylor P-inethYIPhenYIand 7 R1,' R3, B and An .have the meaning indicated in the formula II. I

Amongst these, particularly preferred dyestuffs are those of the general formula R denotes hydrogen, methyl or phenyland the radicals R R R and An have the meaning indicated in the .formulae III or IV.

m (IX) are reacted in an acid medium with epoxides of the' formula In the formulae IX and X the symbols have the meaning indicated in the formula I.

Possible salts'of azo bases' are the salts which arise during diazotisation and coupling in accordance with known processes, as well as the salts Obtained therefrom by anion exchange, for example in the course of working-up and isolation. It is however also possible, using known processes, to liberate the azo' base from thecoupling product first produced by means of acid-binding agents and then to react it with epoxides in the presence of acid agents.

Possible substances with an acid action are: formic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, propionic acid, fi-chloropropionic acid, butyric acid, succinic acid, malonic acid, glutaric acid,-lactic acid-or benzoic acid. The acids can be used individually or as mixtures or conjointly with solvents such as water, benzene, chlorobenzene, acetone or chloroform, dioxane, acetic acid ethyl ester, acetic acid glycol monoester, acetic acid glycol diester, acetic acid polyglycol monoester and diester, acetic acid methyl ester or sterically hindered alcohols, such as tert.-butanol. As acid constituents, inorganic compounds such as hydrochloric acid, sulphuric acid, phosphoric acid, ZnCl or BF optionally also as the etherate, phenol adduct or acetic L acid adduct, can be added in addition to the carboxylic acids mentioned.

Formic acid, acetic acid, lactic acid and propionic acid may be singled'out as particularly suitable carboxylic acids. 1

Amongst the mixtures of acids and solvents there may be mentioned the mixtures of the abovementioned carboxylic acids with water, acetic acid ethyl ester, acetic acid glycol monoester, acetic acid B-methylglycol' mono ester,-- acetic acid diglycol-ether .monoester and diester, acetic acid polyglycol-ether monoester and diester, acetic acid di-(fl-methylglycol)ether monoester and diester, acetic acid -poly-(fil-methylglycol)-ether monester and diester, monoacetic, diacetic and-triacetic acid esters of glycerine'and mixtures thereof. Further suitable mixtures .to be mentioned are those'of the abovementioned carboxylic acids, their methyl and ethyl esters and their monoesters and diesters with glycol, diglycol-ether or polyglycol-ether, with chlorobenzene. I I

- A particularly; preferred embodiment is the reaction in anhydrous carboxylic acids, optionally in the presence of acid inorganic components, such as can for example arise 'if in placeof the free'azo base a salt of the azo base and an inorganic acid is employed. The inorganic component can also be added directly. Particularly suitable carboxylic acids for the anhydrous alkylation are formic acid, acetic acid, lactic acidand propionic acid. Possible inorganic components, optionally bonded to the azo base as a salt are: hydrochloric acid, HB, HF, HI, H SO H3PO4, ZnCl ZIIBI'z and BF3. ,7

The temperature range in which the reaction with epoxides can be carried. out lies between 20 C. and 200 C., preferably between 60" C. and 120 C. Suitable epoxides are, for "example: ethylene oxide, propylene oxide, 1,2-butylene oxide, 1-chloro-2,3-epoxypropane, 1- methoxy-2,3 epoxypropane, 1-ethoxy-2,3-epoxypropane, 1-allyloxy-2,3-ep'oxypropane, 1 phenoxy 2,3 epoxypropane, 3,4-epoxybutene-l, 3,4-epoxypentene-l, cis-epoxy succinic acid and 2,3-epoxybutyric acid alkyl esters. Amongst these, ethylene oxide and propylene oxide are particularly suitable; and amongst the tWo latter ethylene oxide has proved particularly advantageous. If unsymmetrical epoxides are employed, mixtures of dyestufi's according to the formula I can be produced.

The reaction is generally carried out by dissolving, or partially dissolving, the dyestutf base or the dyestutf salt in the abovementioned solvent or solvent mixture. After reaching the desired reaction temperature, the epoxide is addedlt can be in the form of a gas or liquid. In

small batches, the epoxide can be introduced inthe form of a gas, without use of pressure; On an industrial scale, the reaction" ispre'ferably carried out" under slightly elevated pressure (0.'22 a'tmospheres' gauge). At low temperatures,particularly, it is necessary to watch for complete reaction of the epoxide already during theaddition'. In the case of sensitivedyestuffs, or if the dyestuff salts show particular solution'behavior, the epoxide and the carbox'ylic'acidcan be added simultaneously. The epoxide is frequently, like the carboxylicacid, added in a molar excess, since it can be assumed that side-reactions with the'carboxylic acids will occur. The glycol esters which may be produced are good solvents, so that their formation does not cause any problem. and may even be desirable in thecase ofliquids. The end of the reaction is detected by the customary test ofsolubility-properties andby analytical methods, especially by chromatography. Salts of azo bases of: the formula IX can be manufactued in accordance with various methods. For example, the compounds T t I .Ri' 'denotesalkyl, aralkyl, aryl or cycloalkyl and 3X,

1 and m have the meaning indicated in the formula IX,

are manufactured by couplinga methylene base of the f r ula; i

or its salts, in accordance with known ,rnethodspwith diazoniurn salts of suitable amines. The free azo bases can beobtained fromthe resulting coupling products in acalif-CH;

iEL-Ra H-Ra (gH H it is also possible to react azo bases of indolenines of the formula or salts of these azo bases, in an acid medium, with epoxides of the formula In the formulae Ila, XIII and XIV the symbols have the meaning indicated in the formula II.

The compounds of the formula XIII can be obtained according to methods which are in themselves known, by coupling indolenines with diazonium salts and liberating the azo base from the coupling product by means of acidvbinding agents, such as alkali.

The temperature range in which the reaciton with epoxide's can be carried out is between 20 C. and 200 C., preferably between 60 C. and 120 C. As solvents or acids,'it is possible to use the substances indicated in connection with the epoxidation of the compound IX.

Examples of suitable coupling components for the manufacture of compounds of the formula XIII are:

2,3,3,trimethyl-indolenine, 2-methyl-3,3-diethylindolenine, 2,3,3,S-tetramethylindolenine, 2,3,3-trimethyl-5-chloro-indolenine, 2,3,3-trimethyl-5-carboxy-indolenine, 2,3,3-trimethyl-S-cyclohexyl-indolenine, 2,3,3,7-tetramethyl-S-cyclohexyl-indolenine, 2,3,3-trimethyl-5-trifluoromethyl-indolenine, 2,3,3-trimethyl-5-methoxyindolenine, 2,3,3-trimethyl-5-sulphamoylindolenine, 2,3,3trimethyl-5-phthalimidomethyl-indolenine, 2,5-dimethyl-3,3-diethylindolenine, 2-methyl-5-chloro-3,3-diethylindolenine, 2,3,3-trimethyl-5,6-benzoindolenine,

2,3 ,3trimethyl-S-ethoxy-indolenine, 2,3,3-trimethyl-S-butoxy-indolenine, 2-methyl-3,3-diethyl-5-methoxyindolenine, 2-methyl-3 ,3-diethyl-S-carboxy-indolenine, Z-methyl-3,3-diethyl-S-carbomethoxyindolenine, Z-methyl-3,3-diethyl-S-carboethoxyindolenine, 2,3,3-trimethyl-6-chloroindolenine, 2,3,3-trimethyl-7-chloroindolenine, 2,3,3-trimethyl-S-fiuoroindolenine, 2,3,3-trimethyl-5-carbomethoxyindolenine,

l 4 2,3,3-trimethyl-S-ethylindolenine, 2,3,3-trimethyl-S-dodecylindolenine,

2, 3,3-trimethyl-S-n-butylindolenine,

2,3,3-trimethyl-S-n-propylindolenine,

2,3,3-trimethyl-S-benzylindolenine,

2-methyl-3,3 ,S-triethylindolenine,

2-methyl-3,3-diethyl-5-n'propylindolenine,

2-methyl-3,3-diethyl-5-dodecylindolenine,

2,3,3-trimethy1-S-chloro-6-phthalimidomethylindolenine,

2,3,3 ,5-tetramethyl6-phthalimidomethylindolenine,

2,3,3-trimethyl-S-hexahydro-phthalimidomethylindolenine,

2,3,3-trimethyl-S-cyanoindolenine,

5-chloro-6-fluoro-2,3,3-trimethylindolenine,

2,3 ,3-trimethyl-6,7-benzoindolenine,

2,3,3-trimethyl-4,S-benzoindolenine,

2,3,3-trimethyl-5-rnethylmercapto-indolenine,

2,3,3-trimethyl-S-methylsulphonylindolenine, and

2,3 ,3-trimethyl-S-acetylaminoindolenine.

Possible amine components for the manufacture of compounds of the formulae XII and XIII are the amines mentioned for the manufacture of the compounds DCa.

The dyestuffs according to the invention as a rule remain in solution in the reaction medium. They can also be isolated in accordance with known methods, such as distilling off the solvent or other volatile components, salting-out or precipitation. It should be mentioned as being particularly advantageous that following the method according to the invention the dye-stuff is obtained, for example in the case of epoxidations in formic acid, acetic acid, lactic acid or propionic acid, in a solvent which is partially or wholly miscible with organic solvents or with water and which can be used directly for dyeing. The water-miscible solutions which are obtained by reaction of azo bases or their salts with ethylene oxide or propylene oxide in formic acid, acetic acid, lactic acid or propionic acid, and the dyestufr content of which is advantageously between 5 and 50 percent by Weight, should here be singled out particularly. The solutions can also be used whilst employing additives: which are in themselves known and methods, which are in themselves known, for dyeing in organic solvents, such as trichloroethylene or perchloroethylene.

Because of their good solubility the dyestuffs according to the invention are particularly suitable for the manufacture of liquid formulations.

The ready-to-use solutions of the dyestuffs can also be obtained advantageously if the solvents present during the reaction, such as ethyl acetate, chloroform, benzene or chlorobenzene are distilled off for re-use and the dyestutf solutions are replaced by other solvents which are used for the manufacture of liquid dyestuffs.-

Water, lower alcohols, glycols and glycol ethers, for example methanol, ethanol, n-propanol, isopropanol, glycol, propylene glycol, diethylene glycol and triethylene glycol should be particularly mentioned in this context.

The compounds of the general formulae I to VIII are valuable dyestuffs which are in particular suitable for dyeing flocks, fibres, filaments, tapes, Woven fabrics or knitted fabrics of polyacrylonitrile or of copolymers of acrylonitrile with other vinyl compounds, such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl acetate, vinyl alcohol, acrylic and methacrylic acid esters and amides and asymmetrical dicyanoethylene, or flocks, fibres, filaments, tapes, Woven fabrics or knitted fabrics of acid-modified aromatic polyesters. Acid-modified aromatic polyesters are, for example, polycondensation products of sulphoterephthalic acid and ethylene glycol, that is to say polyethylene glycol terephthalates containing sulphonic acid groups (type Dacron 64 of E. I. du Pont de Nemours and Company), such as described in Belgian patent specification 549,179 and US. patent specification 2,893,816. The dyestuffs are furthermore suitable for dyeing acid-modified polyamide.

15 Dyeing can also be effected from a weakly acid liquor, in which case the material is suitably introduced into the dyebath at 40-60 C. and then dyed at the boil.

tized 4+aminodiphenylmethane. The resulting solution of the dyestufi of the composition Furthermore, the dyestuffs can be added to spinning so- CH: (t) lutions for the manufacture of fibres containing poly- 5 acrylonitrile or be applied to the unstretched fibre or wetspun fibre. The dyeings on material containing acrylonitrlle are dlstlngulshed by very good fastness to llght, 1 5

wet processing, rubbing and sublimation. The good levelling capacity of the dyestuffs generaly makes it possible CHIOH to dispense with the use of retarders. (Cm- 0. l)

The dyestulfs are furthermore suitable for dyeing and printing materials of leather, tannin-treated cotton, cellu- 1n aqueous liquors dyes fabrics of polyacrylonltrlle m lose, synthetic polyamides and polyurethanes and ligniny ll w Shadfis of g fKStIIPSS llght and Processingcontaining fibres, such as coir, jute and sisal. They are If half the y 5011mm} 1S llljfroducqd Into 400 furthermore suitable for the manufacture of writing Of Water and rendered alkaline Wlth SOdlLlXIl hYdIOXlde fluids, inks for rubber stamps and ball-pen pastes and can s t and the 011 whlch has separated out is taken also be used in flexographic printing. up 111 benzene/llgrom, and the benzene/hgrom phase is With anionic precipitants such as alumina, tannin, stll'r d with approx. 1570 strength aqueous hydrochloric phosphotungstic and phosphomolybdic acid the dyestuffs Hold, gof the Chloflde of the aljlove'mentloned y form light-fast pigments which can be employed ith adstulf precipitate as yellow crystals WhlCh are recrystallized vantage in paper printing. from water 1n the presence of charcoal. The chloride thus obtained also dyes fabrics of polyacrylonitrile in yellow EXAMPLE 1 shades of good fastness to llght and to wet processmg.

Ethylene oxide is passed for 8 hours at 100 through If the components mentioned in the table are used as a solution, in 200 g. of glacial acetic acid, of 10' g. of indicated in Example 1, dyestulfs or dyestutf solutions the azo base hydrochloride obtained by coupling 1,3,3- are obtained which dye polyacrylonitrile in the color trimethyl 2 methylene-2,3-dihydr0indole with diazoshades given below.

Amine component Methylene component Epoxide Anion Color shade Aniline 1,3,3-trimethyl-2-methylene-2,3-dlhydroindole Ethylene oxide Formatenn Yellow.

Do 1,3,3-trimethyl-5-chloro-2-methylene-2,3- -do Acetate- Do.

dihydroindole. p-Tnlnirlirm do do (10 D0. p-Anisldine do do do Reddlsh-tinged yellow.

p-Phenetldine do do do Do.

Do 1,3,3-trimethyl-2-methylene-2,3-dihydroindole do Formate Do. 1,2,3,4-tetrahydro-5-amlno-n nh h l n do 01H Yellow l-aminonaphthalene do (in H 4-) DO, -amlnodiphenylether..- do do HSO4(-) Red lilish-tinged ye ow. -aminodiphenylsulphldm do do Propionate. Yellow. 4-amino-N-methyldlphenyl-methmm rln (in do Yellowishtinged red. 1-amino-5-benzyloxynapnthalpne do do dn Redclilish-tinged,

ye 0W. 4-aminodipheny ulnhrme do Yellow. 4-amlnodibenzylsulphone do do do Do. 3-aminodipheny do Propylene oxlde Laetate Do. a m m m OXlflH do do i do Reddifih-tinged 3-amin0-9-methyl-carbazole do dn do Yellowishtinged red. 4-amlnobenzophennne do do do Yellow. 3-amino-9-propyl-carham1e do do Acetate Yellowlshtinged red. 2-amino-3-methoxydiphenylene oxide rin Ethylene oxide do Redtfiish-tinged ye ow.

Do..." Propylene oxide do Do. 4-amino-4-hydroxydiphenylmethtine rin Ethylene oxide. ZnCh Yellow. kamino-Q-hydroxy-(2,2)-diphenylpropane dn dn D p-Tnlniflinfi do Propylene oxide.-- Do. p-Anisidine do do Do. l-aminonaphthalene do do Do. 4-aminodiphenyl-ether-.- do do S04(- Reddish-tinged ellow. 4-amlnodlphenyl-sulphone. do do C1() Y llow. 3-amino-9-ethylearbazole do do Cl(-) Yellowishtinged red. 3-aminobenzolc acid dn Ethylene oxide Acetate Yellow. 1amino-4-tert.-butylbenzene do Propylene Xide Cl(-) D0.

Do do Ethylene 0xide. Cl(-) Do. l-amlno-3,4-dlethoxybenzene. do Propylene oxide--- 01H Redgish-tlnged ye ow. l-aminodlphenylmethane 1,3,3-trlmethyl-5-ehloro-2-methylene-2,3- do Cl Yellow.

dihydroindole. 3-amino-9-ethylcarbazole. do do Cl() Yellowishtinged red.

Do l,3,3-trimethyl-5-carboxy-2-1nethylene-2-3- do (11 D0.

dihydroindole.

D 1,3,3-trimethyl-5-carboethoxy-2-methylene-2, do Cl Red.

3-dihydroindole. 2-amino-3-methoxydlphenylene oxide 1,3,B-trimethyl-S-carboxy-2-methylene-2,3- Ethylene oxide..." Acetate Yellowishdlhydroindole. tinged red. 3-amlnophenylpropionic acid 1,3,3 trimethyl-2-methylene-2,3-dihydroindole .do. ellow. 3-aminobenzo do do Do. Z-aminobenzolc acid 2,3-dimethylbenzothiazoliummethosulphate do Do.

sulphate.

1 7 EXAMPLE 2 Ethylene oxide is passed for 10 hours at 100 through a solution, in 20Q g. of glacial acetic acid of 10 g. of azo base obtained by coupling 1,3,3-trimethyl-2-methyleneindoline with p-tolui-dine and treatment of thecoupling product with alkali. The resulting solution of the dyestuif of the composition in aqueous liquors dyes fabrics of polyacrylonitrile in yellow shades of good fastness to light and to wet processing.

EXAMPLE 3 Ethylene oxide is passed for 7 hours through a solution, in 150 g. of glacial acetic acid, of g. of azo base obtained by coupling S-nitro-1,3,3-trimethyl-2-methylene- 2,3-dihydroindole with diazotised 3,4-diisopropoxyaniline and treatmentof the coupling product with alkali. The resulting solution of the dyestulf of the composition in aqueous liquors dyes fabrics of polyacrylonitrile in scarlet-red shades. If the procedure indicated in Example 1 is followed, the chloride of the dyestuif is obtained in red crystals viathe carbinol base by reaction with hydrochloric acid. Yield 2.5 g.

EXAMPLE 4 20 g. of azo base obtained by coupling 1,3,3-trimethyl- 2-methylene-2,3-dihydroindole with diazotized 4-aminoazobenzene and reaction of the coupling product with alkali, are dissolved in 200 ml. of glacial acetic acid.

Ethylene oxide is passed into the solution for hours. The resulting solution of the dyestuii of the composition in aqueous liquors dyes fabrics of polyacrylonitrile in strongly reddish-tinged yellow shades of good fastness to light and to wet processing.

EXAMPLE 5 10 g. of azo base obtained from 1,3,3-trimethyl-2-methylene-2,3-dihydroindole and 3-an1ino-9-ethylcarbazole are dissolved in 250 ml. of glacial acetic acid and ethylene oxide is passed into the solution at 100 for 7 hours. The reaction mixture is introduced into ice-water and after addition of 100 ml. of benzene is rendered alkaline with 20% strength sodium hydroxide solution Whilst stirring. After addition of 60 ml. of approx. strength hydrochloric acid, 2.0 g. of the dyestufi are obtained in redviolet crystals from the benzene phase. The dyestufi, which can be further purified by recrystallization from water in the presence of charcoal, corresponds to the fomula and dyes fabrics of polyacrylonitrile in scarlet-red shades.

If the solution obtained by the reaction with ethylene oxide is used for dyeing, dyeings of scarlet-red shades of good fastness to light and to wet processing are again obtained on polyacrylonitrile, with the color strength corresponding to complete conversion of the azo base to the alkylated dyestuff.

EXAMPLE 6 20 g. of thedyestutf base of the formula CH: @N

. ethylene oxide is again passed in. Dissolved ethylene oxide is removed by again distilling. The residue is made up to g. with water, and filtered. An approx. 25% strength solution of the 'dyestufi of the formula is obtained. The solution of the dyestutf can be measured out easily and polyacrylonitrile fibres and acid-modified polyester fibres can be dyed with it in a'strong yellow shade.

EXAMPLE 7 20 g. of the dyestuif base of the formula I Gin-N NClh are dissolved in 200 g. of acetic acid and ethylene oxide is slowly passed through the solution for 12-14 hours at 40-60 C. Thereafter, dissolved ethylene oxide is removed in vacuo and a part of the acetic acid is distilled oif. An approximately 10% strength solution of the dyestuif of the following formula CH3-N N C Ha U-CH=N O21. C 11 GH -COOP) 43H: (B =1. C 11 I 19 20 is obtained in an acetic acid/acetic acid glycol ester mixare dissolved in 100 g. of acetic acid and 60-70 g. of ture. The solution of the dyestuff dyes fabrics of poly propylene oxide are slowly added dropwise at 50-60 C. acrylonitrile, in an aqueous liquor, in red-yellow shades. so that the mixture barely refluxes. Over the course of The solution, on addition of aqueous ZnCl solution, 14-16 hours, the mixture reacts to give a product which yields the ZnCl salt in the form of greenish crystals. 5 is probably a mixture of the following two components:

EXAMPLE 8 10 g. of the dyestuff base of the following formula O A 10 CH3-N fI-CHS CHr-N NCH;

| 0 VCH=N-N 011,- CHN=N A cmooow C H3- 0 1 5 (I l H 0 H CHa are dissolved in 100 g. of acetic acid. Ethyleneoxide is and passed into the solution at 45-55 C. until the acetic acid 0 has been largely consumed, which as a rule is the case after approx. to 12 hours. The resulting solution of A 0 the dyestutf of the formula CHa-N N-CH: CHSCOOH O iL 5 CHr- H CHr-N N-OH: I

HzOH c 000M CHaK/ CH=N-E o\ 2CH3O- The dyestutf solution dyes fabrics of polyacrylonitrile, HZOH in an aqueous liquor, in red-yellow shades.

The dyestuff solution can be freed of a part of the solvent by distillation in vacuo and can be employed in a concentrated form for dyeing. If 20 ml. of the dyestuff in acetic acid glycol ester/acetic acid dyes fabrics of polyacrylonitrile in red-yellow shades.

EXAMPLE 9 solution are mixed with 60 ml. of water and 30 ml. of 10 g. of the following dyestufi base 5% strength aqueous hydrochloric ac1d, 2.2 g. of the 0 chloride of the dyestuff precipitate in the form of orangered crystals. A 0 If the components mentioned in the table are treated cm-N N-CHS as indicated in Example 9, dyestuffs or dyestuif solutions are obtained which dye fabrics of polyacrylonitrile in the OHN=N color shades indicated.

Amine component. Methylene component Epoxide Anion Color shade a-amlno-tl-ethyleerbazole 1,3,fi-trimethyM-methylenepyrlmldone-(2)...- Ethylene oxlde... Acetate Red. 4-erninodlphenylmethonedo do Lactate Redg'sh-tlnged ye ow. 3-emlnodlphenylmethenee do do do Do. a-amlnodlphenylene xi e do do Acetate Strongly reddish-tinged yellow. 2-amlno-3-metl1oxydiphenylene mime do Propylene oxide do Do. kaminodiphenyl-ether do -do 01H- Redrllllsh-tlnged ye ow. l-amlne-4-methylsulphonylbenzene .do Cl Do. tamino-N-methyldlphenyl m Ethylene oxlde... Cl Red. B-emlno-Q-ethylearbazole d do 01H R d, D 1, (2) ..do Cl Red. ll-amlnodlphenylene nflde do 01 Strongly reddish-tinged yellow. B-aminodiphenylene sulphide. .do d0..... 01 Redldllsh-tlnged ye ow. t-aminodlphenyl-ether e do do Cl Strongly reddish-tinged yellow. 4-amlno-4'-l1ydroxydlphenylmethen e do do Y 01 Redgish-tlnged e ow. p-Toluldlne r e do Propylene oxide..- 014- y D0. 4-amlnodlpheny e do Ethylene oxide CK" Do. 4-am1no-4-nltrodlpheny1methene do do 01 Do. p-Anisldinn do CK Strongly reddish-tinged yellow. A m do I we d 7 c1(-) Reddish-tinged yellow. p-Tnlnifllnn do Propylene oxide..- 01 Do. l-amlnonephtholene- .do .do l Do.

Do .do Ethylene oxlde Do. 4-ernlnodipheny nlnhnn do .d Do. 1,2,3,ktetrahydro-5-aminonaphthalene ..d0 Do. pJPhpm-ifldlfln do do Do Do .do Propylene oxide Do. aminmwntnnlliflfl dn Ethylene oxide ClH Strongly reddish-tinged yellow.

1emino-3,4-dllsopropoxy nv n do .do Cl Do. p-Chlormniline do .-do. 01 Redgish-tlnged e ow. 4-aminohmwnnhnnn'nn do do (116-) y D() B-amino-4-methylbenzophenone .do. Do.

21 22 EXAMPLE 10 dyes fabrics of polyacrylonitrile in an aqueous liquor in (a) Manufacture of the coupling prod t f reddish-tinged yellow shades of good fastness to light and to wet processing.

If the procedure indicated in Example 10 is followed 107 g. of p-toluidine in a mixture of 310 ml- Of c and the appropriate components are used, dyestuffs or centrated hydrochloric acid and 4,000 ml. of water are 5 dyestuif solutions can be obtained which dye fabrics of diazotized at C. with approx. 300 m1. of 30% strength polyacrylonitrile in the color shades indicated.

2,3,3-trimethylindolenine and p-toluidine Amine component Indolenine Epoxide Anion Color Shade Aniline 2,3,3- rimethylindolenine- Ethylene oxide.... Acetate Yellow. p-Anisidine ..do o ..do Redfish-tiuged ye ow. 4-aminodiphenylsu1phone (10 do -do Yellow. 4-aminodiphenyl-ether. -.do. Propylene oxl .do- Redflish-tiuged ye ow. a-Arninodiphenyl-ether. -d0 .do. Do. p-Phenetidine do Ethyleu Do.

Do -chloro-2,3,3-tzlmethylindolenine .do Do. 9-ethyl-3-an1inocarbazole-.- Propylene oxide Orange-red. 4-aminobenzophenone- -do ellow.

o. do Ethylene oxide. Do. Z-amiuodiphenylene oxide. Propylene oxide do Rediilishtinged e ow. p-Tnlniriinn 5-Methoxy-Z,3,3-trlmethylindolenine Ethylene oxide ..do y Do.

Do. ..d0 Propylene oxide. do. D0.

. 5-eyclohexyl-2,3,3-trimethylindolenine. Ethylene oxide-. .do. Yellow. 2,3,3,5-tetramethylindolenine do do... Do. 2,3,3trimethylindolenine .do -do Do. 5-carboxy-2,3,3-trimethylindolenine. do .do Redgish-tinged ye ow. 5-methylsulphonyl-2,3,3trlmethyllndolenine do ..do Yellow. 2,3,3-trimethylindolenine Propylene oxide. ---do Do. 5-benzyloxy-2,3,3-trimethylindolenine Ethylene oxide.. .do- Do. 5-cyclohexyl-2,3,B-trimethylindolenine. do do Do. 5-methoxy-2,3,3-trimethylindolenine .-do do Stronglyregdishtinge yellow. 5-earboxy-2,3,3tr1methyllndoleniue do .do Do. 5-cyano-2,3,3-trimethylindolenine. do do Yellowishtinged red. 1,2,3,4-tetrahydro-5-amlnonaphthalene 5-methoxy-2,3,3-trlmethylindolenine Propylene oxide do Redflish-tinged ye ow.

Do- 5-ch1oro-2.3,3-tnmethylindolen1ne Ethylene oxide ..do--.-.--- Yellow. 4-Ethylanilineo .do. .do Do.

Do. 2,3,3-trlmethyhndolenin d e-umlno-N ethyldiphenyl-amineo.-.

4-amino-4-ethoxy-N-methyldiphenylamlne .do

Do. 5-chloro'2,3,3-t1imethylind 9-ethyl-3-aminocarbazole. 2,3,3,5tetramethylindolenine.. 3-aminodiphenylenesulphate. 2,3,3-trimethylindolenine Do. l 5-trifluoromethyl-2,3,3-trimeth nd 1-amino-5-methoxynaphthalene 2,3,3trimethy1indolenine 1-amino-5-benzyloxynaphthalene ..do 4-dodeeylaniline 5-methoxy-2,3,3-trlmethylindolenine. 3,4-dlmethoxyaniline 2,3.3trimethylindolenine -aminodiphenylsulphone 5-chl0r0-2,3,3-trimethylindolenine a-nmino-4-methoxyphenylbenzylsulphone 2,8,3-trimethylindolenine D 2 4.djeth0xyani1jne 5-chloro-2,3,3-trimethyhndolenine Reddish-tinged ellow. -aminoazobenzene- 2 y 4,4-diaminodiphenylmethane Yellow. 4-amino-4'-hydroxy-2,2-diphenylpropsne.- ...do D 4-aminoazobenzene 6,7benzo-2,3,3trimethylindolenine do do Strongly reddish-tinged yellow.

by volume sodium nitrite solution, and excess nitrite 1s EXAMPLE 11 then destroyed by means of amidosulphonic acid. Thereafter, following the addition of S g. of an emulsifier, 159 (a) Manufacture of the coupling product of 4-aminodig. of 2,3,3-trirnethylindolenine are added dropwise over phenylmethane and 2,3,34rimethY1indo1enine the course of /2 hour, and the mixture is adjusted to pH 5 Over the course of 6 hours y adding sodium acetate 55 92 g. of 4-aminodiphenylmethane in a mixture of 160 The mixture is stirred for 3 hours at this pH and is then adof concentrated hydrochloric acid and 1 000 m1 of justed to pH 9 with 10% strength sodium hydroxide soluat d t 00 C f tion. The free azo base which has precipitated is recrystal- W er are a 1 W1 P 9. lized from alcohol with the addition of approx. 3% by vol- Stfength by Y l Sodlum llltfltf 501110011: After ume of 10% strength sodium hydroxide solution and is destroying EXCESS mime y means of amldoslllphonlc acid,

obtained in yellow crystals. Yield: 230 g. 79 g. of 2,3,S-trimethylindolenine are added dropwise over 1, Reaction of the azo base with 2 mols the course of 1 hour and the mixture is neutralised with of ethylene oxide 10% strength sodium hydroxide solution, initially slowly and subsequently more rapidly, to pH 4-5 over the course 19 g of he free azo base are dl'ssolYed m 200 m1. of of a total of 15 hours The azo base h drochloride which glacial acetic ac1d and ethylene oxide 1s passed through Y the solution at 100 C. for 8 hours. The resulting soluhas precipitated 1s filtered olf, washed with 5% strength tion of the pure dyestulf of the formula sodium chloride solution and dried in vacuo at 50 C.

cm Yield 125 g.

(b) Reaction of the azo base hydrochloride with 2 mols N cH= Iz CHrof ethylene oxide (EHPCHPOH F Ethylene oxide is passed through a solution of 20 g. of

razo base hydrochloride in 200 ml. of glacial acetic acid 3 for 7 hours at 100 C. The resulting solution of pure dyestuff of the formula I CHg-CHz-OH (H OH dyes fabrics of polyacrylonitrile in an aqueous liquor in 10 reddish-tinged yellow shades of good fastness to light and to wet processing.

EXAMPLE 12 (a) Manufacture of the coupling product of 2,3,3-tri- 15 methylindolenine and Z-aminodibenzofurane 43.8 g. of 2-aminodibenzofurane hydrochloride are dissolved in a mixture of 64 ml. of concentrated hydrochloric acid and 800 ml. of water at 60 C. and the fine crystal paste which is produced at 0 C. is diazotized with 39 ml. of 30% strength by volume sodium nitrite solution. After adding 1.2 g. of emulsifier, 31.6 g. of 2,3,3-trimethylindolenine are added dropwise and the mixture is then adjusted to pH 4 over the course of 4 hours by means of 5% strength aqueous sodium hydroxide solution at stirred for a further 10 hours at room temperature. The crude azo base hydrochloride which has precipitated in reddishyellow crystals is recrystallized from benzene. Melting point: 232234 C., yield: 35.0 g.

-('b) Reaction of the azo base hydrochloride with 2 mols of ethylene oxide 10 g. of azo base hydrochloride are dissolved in 250 ml. of glacial acetic acid and ethylene oxide is passed through the solution for 9 hours at 90-95" C. The dyestuff solution is mixed with a 5-fold volume of ice/water, and then with 5% strength hydrochloric acid and with aqueous ZnCl solution. The dyestuff Which has precipitated in reddish-yellow crystals is recrystallized from 40 water with the addition of charcoal. 3.6 g. of the dyestufi? of the formula are obtained. It dyes fabrics of polyacrylontrile in strongly reddish-tinged yellow shades of good fastness to light and to wet processing.

If the procedure indicated in Example 12 is followed and the appropriate components are used, it is possible to obtain dyestuffs or dyestuif solutions which dye fabrics of polyacrylonitrile in the colour shades indicated:

24 EXAMPLE 13 (a) Manufacture of the coupling product of 9,9,9a-trimethyl 2,3,9,9a tetrahydrooxazolo [3,2a] indole and 4-aminodiphenylmethane.

which precipitates in reddish-yellow crystals is washed with 5% strength aqueous sodium chloride solution and then dried in vacuo at 50 C. Yield: 140.0 g.

(b) Reaction of the azo base hydrochloride with 1 mol of ethylene oxide 10 g. of the azo base hydrochloride are dissolved in 200 ml. of glacial acetic acid and ethylene oxide is passed through the solution for 8 hours at C. The reaction mixture is introduced into a mixture of 900 ml. of 5% strength hydrochloric acid and 2,000 g. of ice/water. 4.6 g. of the dyestuff precipitate as yellow crystals after prolonged stirring. The dyestulf corresponds to the formula a -w-Q- -Q CH and dyes fabrics of polyacrylonitrile in reddish-tinged yellow shades of good fastness to light and to wet processing.

If the procedure indicated in Example 13 is followed and the appropriate components are used, dyestuffs or dyestuif solutions are obtained which dye fabrics of polyacrrylonitrile in the shades indicated.

Amino component Indolenine Epoxide Anion Color Shade l-aminonaphthalene 2,3,3-trimethylindolenine Ethylene oxide Chlorozineate- Yellow.

Do 5-chloro-2,3,3-trimethylindolenenedo do Do. 4-amlnodiphenylruethanedo do do Q-ethyl-B-aminoearbazoledo do do Orange-red, Z-aminodlphenylene oxide do do do Reddishtinged ellow. 1-amlno-4-tert.-buty lbenzene 2,3,3-trlmethylindolenine. Propylene oxide do Ygllow. 3,4-ddsopropoxyamlme. Ethylene oxide .do Strongly reddishtinged yellow. p-Anisjdlnh 2,3,3,5-tetramethylindolenine..;.: Propylene oxide.-..-.;..d0 Reddishtinged 1,2,3,4-tetrahydro-f -amlnonaphthalene 2,3,3-trimethyllndnlenine Ethylene xi do Y liia svfi 4-amjno-N-ethyl-diphenylam1ne 5-ehloro-2,3,3-trlmethylindolenine do do Yellowishtin ed red; 9-methyl-3-amlnocarbazole do Propylene oxide do Orange-red.

Do 5-carbomethoxy-2,3,B-trlmethylindolenlne. Ethylene oxide do Bluishtinged 9-ethyl-3-amlnooarbazole. do do do 1 50. 3-amlnodlphenylenesulphide 5-chloro-2,3,3-trlrnethylindolenlne .-do "do Yellow. Lemme-5-methoxynaphthelene 5-methoxy-2,3,3-trimethy l nin do do Strongly reddisfil-tlnged 3-amlno-4-methoxyphenylbenzylsulphone 5-ethyl-2,3,3-trimethyllndolenine do do Ygl losv i Amino component Oxazolo-[3,2al-indole Epoxide Anion Color shade Zi-aminodiphenylene oxide 7,9,9,9atetramethyl-2,3,9,Qa-tetrahydrooxazolo- Ethylene oxide Cl- Reddish-tinged [3,2 -indole. yellow.

3-aminodiphenylene sulphide 7-ehloro-9,9,Qa'trimethyl-Z,3,9,9a-tetrahydro- Propylene oxide 01' Yeloow.

oxazolo-[3,2a]-indole.

-aminodiphenylmethane 5,6-benzo-9,9,9atrimethyl-2,3,9,9a-tetrahydro- Ethylene oxide Cl- Strongly red oxazolo-[3,2a]-indole. dish-tinged yellow.

i-aminodiphenyl-ether 7-earboxy9,9,9a-trimethyl-2-phenoxymethyl- -do 01- Orange.

2,3,9,Qa-tetrahydrooxazolo-[3,2a]-indole.

l-aminonaphthalene 7-cyclohexyl-5,9,9,9,a-tetramethy1-2,3,9,9ado 01- Yellow.

tetrahydrooxazolo-[3,2a]-indole.

2-a1nino-3-methoxydiphenylene oxide- 7-mothoxy-9,9,Qa-trimethyl-2,3,9,9a-tetrahydro- Butylene oxide- Cl- Reddish-tinged oxazolo-[3,2al-indole. (1,2) yellow.

4-amino4-ethoxy-N-methyldiphenylamine 7,9,9,9a-tetremethyl-2,3,9,9a-tetrahydrooxazolo- Ethylene oxide Cl Yellowish- [3,2a1-indole. tinged red.

EXAMPLE 14 (a) Coupling product of 9,9,9a-trimethyl-2,3,9,9a tetrahydroxazolo[3,2-a]-indole and 9-ethyl 3 aminocarbazold 66.5 g. of 9-ethyl-3-aminocarbazole in a mixture of 90 ml. of concentrated hydrochloric acid and 800 ml. of water are diazotized with 60 ml. of 30% strength by volume sodium nitrite solution; after destroying the excess nitrite, 51.5 g. of 9,9,9a-trimethyl 2,3,9,9a tetrahydrooxazolo-[3,2a]-indole are added and the mixture is then adjusted to pH 3-4 with strength aqueous sodium hydroxide solution over the course of 4 hours. The coupling product which has precipitated is washed with 5% strength sodium chloride solution and dried in vacuo at 50 C.

(b) Reaction of the azo base hydrochloride with 1 mol of ethylene oxide 30 g. of the azo base hydrochloride are dissolved in 250 ml. of glacial acetic acid. Ethylene oxide is passed into the solution for 7 hours at 90-100" C. The resulting solution of pure dyestuff of the formula [GHQ-C00, Gl](-) dyes fabrics of polyacrylonitrile in an aqueous liquor in scarlet-red shades of good fastness to wet processing and to light.

I 2 CHr-CHa-OH 1 CH;- 0 H EXAMPLE (a) Coupling product of 4-aminodiphenylmethane and a mixture of 9,9,9a-trimethyl-Z-allyloxymethyl-2,3,9, 9a-tetrahydrooxazolo[3,2a] indole and 9,9,9a trirnethyl-3-allyloxymethyl 2,3,9,9a tetrahydrooxazolo- [3,2a1-indole 9.5 g. of 4-aminodiphenylmethane are diazotized in a mixture of 16 ml. of concentrated aqueous hydrochloric acid and 200 ml. of water at 0 C. After destroying excess nitrite, 13.5 g. of the tetrahydrooxazolo-[3,2]-indole mixture are added over the course of 1 hour. The mixture is neutralized to pH 4 with 20% strength aqueous sodium acetate solution over the course of 5 hours. The azo base hydrochloride of the formula (IIIH:

which is obtained in red crystals is converted into the azo base by reaction of a 5% strength sodium hydroxide solution.

(b) Reaction of the azo base with 1 mol of ethylene oxide Amine component Oxazolo-[3,2a]-indole Epoxide Anion Color Shade p-Anisidine 7-iluoro-9,9,9a-trimethyl-2,3,9,Qa-tetrahydro- Ethylene oxide Acetate.-. Reddish-tinged oxazolo-[3,2a]-indole. yellow. p-Phenetidine do Propylene oxide --do Do. Do 7-ehlor0-9,9,9a-trimethyl-2,3,9,9a-tetrehydro- .do do Do.

oxazolo-[3,2a]-indole. a-aminodiphenyl sulphide 7-ethoxy-9,9,9a-trimethyl-2,3,9,9a-tetrahydro- Ethylene oxide do Do.

oxazolo-[3,2a]-indole. 4-aminoazotoluene do Propylene oxide -do Do. -aminoazobenzene 7-methoxy-9,9,9a-trimethyl-2,3,9,9a-tetrahydro- Ethylene oxide -do Do.

oxazolo-[3,2a]-indole. 4-aminodiphenylether 7-earboxy9,9,9a-trimethyl-2,3,9,Qa-tetrahydro- Propylene oxide do Orange.-

oxazolo-[3,2-a]-iudole. p-Toluidine 2,9,9,Qa-tetramethylZ,3,9,9a-tetrahydrooxazolo- --.do do Yellow.

[3,2a1-indole. Do 3,9,9,9a-tetramethyl-2,3,9,9a-tetrahydrooxezolo- ..do do. Do.

[3,2a]-indole. Do 2,7,9,9,9aentamethyl-2,3,9,Qa-tetrahydro- Ethylene oxide do Do.

oxazolo- 3,2a1-indole. p-Tnlnidinn 3,7,9,9,9aentamethyl-2,3,9,9a-tetrahydrodo do Do.

oxazolo' 3,2a1-indole.

TABLE-Continued Amine component Oxazolo-[3,2a]-indole Epoxide Anion Color Shade p-Apisidine 9,9,9a-triniethyl-2-ethyl-2,3,9,SJa-tetrahydro- Ethylene oxide Acetate Reddish-tinged oxazolo-[3,2a]-indole. yellow. Do 9,9,9a-trimethyl-3-ethyl-2,3,9,tJa-tetrahydrodo .do Do.

oxazolo-[3,2a]-indole 3,4-diisopropoxyaniline 7-chloro-9,9,Qa-trimethyl-Zfi,9,9a-tetrahydro- Propylene oxide ..do Strongly redoxazolo-[3,2a]-indole. dish-tinged.

yellow.

D i do Ethylene oxide do Do. I-aminonaphthalene. Propylene oxide -do Yellow. l-amino-i-isopropylbenzene 7-methoxy-9,9,9a-trimethyl-2,3,9,Qa-tetrahydro- Ethylene oxide -.do Reddish-tinged oxazolo-[3,2a]-indole. yellow. 2-amino-3-methoxydlphenylene oxide .do .d do Do. m-Anisidine d .do -do Do.

Do 9,9,9a-trimethyl-2,3,9,Qa-tetrehydrooxazolodo .do Do.

[3,2a1-indole. Do 7-chlorc-9,9,9a-trimethyl-2,3,9,Qa-tetrahydrodo -.d

oxazolo-[3,2a]-indole. z-chloroi-aminoanisole 9,0,9a-trimethyl-2-(n-hexyloxymethyl)-2,3,9,9a- Ethylene oxide.-.

tetrahydrooxazolo-[3,2a]-indole. 4-ethy anilin 7,9,9,9a-tetrarnethyl-2,3,9,Qa-tetrahydrodo do oxazolo [3,2a]-indole. Dn 9,9,9a-trin1ethyl-2,3,9,9a-tetrahydrooxazolo- Propylene oxide .do Do;

[3,2al-indole. Dehydrothiotolui Ethylene oxide do Do. 9-ethyl-3-aminocarbazole 9,ifig-aringtliyl-Zfifl,Qa-totrahydrooxazolo- Propylene oxide do orangered.

, a -m o e. D 7-carboxy-9,9,9a-trimethyl-2,3,9,9a-tetrahydro- Ethylene oxide do Bluish-tinged oxazolo-[3,2a]-indole. red. z-ehloro--aminoanisole 9,9,Qa-trimethyl-Z-(n-hexyloxymethyl)-2,3,9,9a- Reddish-tmged tetrahydrooxazolo-[3,2a]-indole. yellow. Aniline 9,9,9a-trimethyl-2-chlorornethyl-2,3,9,Qa-tetra- Yellow.

hydrooxazolo-[3,2a1-indole.

Dn 9,9,9a-trimethyl3-chloromethyl-2,3,9,9a-tetra- Do.

hydrooxazolo-[3,2a1-indole.

Dn 9,9,9a-trimethyl-2,3,9,Qa-tetrahydrooxazolo- Propylene oxide ..do Do.

[3,2a]-indole. o-Anlsidine do 1,2-butylene oxide do Do. Do do Ethylene oxide do D0.

EXAMPLE 16 EXAMPLE 18 A fabric of polyacrylonitrile is printed with a printing paste which was manufactured in the following manner: Polyacrylomtnle fibres are mtroduced usmg a hquor ratio of 1:40, into an aqueous bath at 40 C. which per 20 of the dyestufi of the formula litre contains 0.75 g. of strength acetic acid, 0.38 on, g. of sodium acetate and 0.15 g. of the dyestuff of the Cm formula I CH=N-N-- 33 g. of thiodiethylene glycol, 20 g. of cyclohexanol and cm 20 g. of 30% strength acetic acid are covered with 220 (g g. of hot water and the resulting solution is added to 330 parts by weight of a thickener (gum arabic used as a H aqueous solution of 3% of weight). 20 g. of zinc nitrate solution are added thereto. The print obtained is dried, The h 1S ate to the boil Over the course of 20-30 steamed for 30 minutes and subsequently rinsed. A redfill-flutes. p at temperatul'fi minutesdish-tinged yellow print of good fastness properties is Afltff 1111151118 and y g, a gly s -t ged yellow bt i d, dyeing having very good fastness properties is obtained. EXAMPLE 17 EXAMPLE 19 Acid-modified polyglycol terephthalate fibres are introduced at 20 C., using a liquor ratio of 1:40, into an aqueous bath which per litre contains 3 to 10 g. of sodium sulphate, 0.1 to 1 g. of oleyl polyglycol ether (50 mols 30 g. of polyacrylonitrile fabric are introduced into one litre of a dyebath at -80 C., which contains 0.6 g. of a 10% strength solution of the dyestutr' of ethylene oxide), 0-15 g. of dimethylbenzyldodecylam- O monium chloride and 0.15 g. of the dyestufl? of the H formula 60 CHa-N N-cn,

CH, m I CH -COOH Cm OH=N-E-Oi. 0.111 H 0-1 G H CH=N-N HBOH a 7 n. ZnCl CH; N/ and 0.5 g. of an ethylene oxide adduct of 50 mols of ethylene oxide to 1 mol of oleyl alcohol and which has been CHgOH H adjusted to a pH-value of 4-5 by adding acetic acid. The

dyebath is heated to 98 C. and the temperature is mainand which has been adjusted to pH 4-5 with acetic acid. tained for about minutes whilst frequently swishing The mixture is heated to C. over the course of 30 the fabric. Thereafter, the fabric is washed in a bath minutes and the bath is -kept at this temperature for 60 which contains 1-2 g./l. of a non-ionic detergent (for minutes. Thereafter the fibres are rinsed and dried. A example a nonylphenol reacted with 10 mols of ethylene yellowish-tinged red dyeing of very good fastness properoxide) and is rinsed with water. A light-fast and wash-fast ties is obtained. 75 dyeing in a. yellow-orange-colored shade is obtained.

. alkyl, C -C -alkoxy, phenoxy, benzyloxy, amino,

dialkylamino, sulfamoyl,

29 We claim: 1. Hydrazone dyestuif of the formula in which R, is C -C -alkyl; C -C -alky1 substituted by chloro, fiuoro, methoxy, cyano or hydroxy; phenyl; benzyl; phenethyl or CH-R4 HRs 3 R and R are hydrogen; C c alkyl; C -C -alkyl substituted by chloro, fiuoro, methoxy, cyano or hydroxy; C C -alkenyl; C C alkyloxymethyl; C -C -alkenyloxymethyl or phenoxymethyl; at least one of R or R being hydrogen or C -C -alkyl; R and R are hydrogen; C -C alkyl; C -C -alkyl substituted by chloro, fluoro, methoxy, cyano or hydroxy; C -C -alkenyl; C -C -alkinyl; phenyl; benzyl; c -C -alkoxymethyl; C -C -alkenyloxymethyl; or phenoxymethyl; at least one of R or R being hydrogen or C -C -alkyl; X represents the remaining members of an indoline nucleus, an indoline nucleus having a fused 5- or 6-member carbocyclic ring; a pyrimidone nucleus; a benzothiazole nucleus; 2. quinoxaline nucleus; or a quinazoline nucleus; B is a phenyl nucleus; a tetrahydronaphthalene nucleus; :1 carbazole nucleus; a-diphenylenesulfide nucleus; a diphenylene oxide nucleus; at tetrahydrodiphenylene oxide nucleus; a hexahydrodiphenylene oxide nucleus, a tetrahydrocarbazole nucleus; or a hexahydrocarbazole nucleus; m is a number 1 or 2; and AnE is' an anion.

2. Hydrazone dyestufi of claim 1 having the formula B mint-i oH-R, H-R

H m in which R is hydrogen or one or more members selected from the group consisting of halogen, nitrile, nitro, C -C -alkyl, fiuoromethyl, phenyl, benzyl, C5-C7'CYC1Q I C -C alkylmercapto, C -C alkylsulfonyl, phenylsulfonyl, benzylsulfonyl, carboxyl, Cr'CffllkOXYCQI'bOHYl, carboxy-C C -alkyl, phthalimidooxymethyl; R

R is the residual part of a fused benzene ring; and R and R are hydrogen, methyl, ethyl, chloromethyl, [3- chloroethyl, vinyl, allyl, phenyl, benzyl, methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, isobutoxymethyl, n-hexyloxymethyl, allyloxymethyl, methallyloxymethyl, phenoxymethyl, or 4-methoxyphenoxymethyl; with at least one of R or R being hydrogen, methyl or ethyl.

4. Hydrazone dyestuff of the formula in which R-, is hydrogen, C -C -alkyl, C -C alkenyl, C -C alkyloxymethyl, C -Q-alkenyloxymethyl or phenis hydrogen, C C -alkyl, C -C -alkenyl, C -C,;alkoxymethyl, C C -alkenyloxymethyl or phenoxymethyl, with at least one of the R or R being hydrogen or C C -alkyl; R is methyl, ethyl, n-propyl, n-butyl, cyclohexyl, phenyl, p-chlorophenyl or pmethylphenyl,

R denotes methyl, ethyl, n-propyl, n-butyl, cyclohexyl, phenyl,- p-chlorophenyl or p-methylphenyl; R is hydrogen, methyl, phenyl, p-chlorophenyl or p-methylphenyl; and B is a phenyl nucleus, a tetrahydronaphthalene nucleus; a carbazole nucleus; a diphenylenesulfide nucleus; at diphenylene oxide nucleus; a tetrahydrodiphenylene oxide nucleus; at hexahydrodiphenylene oxide nucleus; a tetrahydrocarbazole nucleus; or a hexahydrocarbazole nucleus; m is a number 1 or 2; and Am is an anion.

5. Hydrazone dyestuflf of the formula I CH;

Rn -CH1 N/ arenas-Q AnH l Ru -Ru H-Rn , wherein 1 C -C -alky1 and a fused benzene ring; a is 0, 1 or 2; and,

b is 0, 1 or 2.

3. Hydrazone dyestuir' of claim 2 in which a is 0; b is 0; R is methyl, ethyl, n-propyl, isopropyl or n-butyl, phenyl, benzyl, p-nitrobenzyl, phenethyl or p-nitrophenethyl R and R are hydrogen, methyl, ethyl, allyloxymethyl or phenoxymethyl; at least one of R or R being hydrogen, methyl or ethyl; R is hydrogen, or one or more substituents selected from the group consisting of fluorine, chlorine, bromine, nitrile, nitro, sulfamoyl, amino, dimethylamino, diethylamino, methyl, ethyl, n-propyl, d0- decyl, methoxy, ethoxy, n-propoxy, n-butoxy, phenoxy, benzyloxy, methylmercapto, ethylmercapto, methylsulfonyl, ethylsulfonyl, phenyl, p-nitrophenyl, benzyl, 4- methoxybenzyl, cyclohexyl, cyclopentyl, trifluoromethyl, trichloromethyl, carboxy, carboxymethyl, carboxyethyl, carbomethoxy, carboethoxy and phthalimidomethyl; or

R denotes methyl or ethyl,

R denoteshydrogen, methyl or ethyl,

R denotes hydrogen, methyl or ethyl,

R denotes hydrogen, chlorine, methyl, methoxy, ethoxy,

benzyloxy, carboxy, carbomethoxy, or carboethoxy,

R denotes hydrogen or one or more methyl, methoxy, ethoxy, i-propoxy, benzyl radicals or together with the phenyl ring denotes a naphthyl, carbazolyl or diphenylene oxide radical and An denotes an anion. I

6. Hydrazone dyestutf of the formula R denotes hydrogen, methyl or ethyl,

R denotes hydrogen, methyl or ethyl,

R denotes hydrogen, chlorine, methyl, methoxy, ethoxy,

benzyloxy, carboxy, carbomethoxy, or carboethoxy,

31 32 R denotes hydrogen or one or more methyl, methoxy, 10. A hydrazone dyestuff of the formula ethoxy, i-propoxy, benzyl radicals or together with the O phenyl ring denotes a naphthyl, carbazolyl or diphenylll ene oxide radical and AI1 denotes an anion. CH N NTCH 7. Hydrazone dyestulf of the formula K) -1-0 N R11 ort, Ru 011,011 a 1 -c =N- 11. A mixture of the hydrazone dyestuffs-of the for- N An mulae R denotes hydrogen, methyl or ethyl,

R denotes hydrogen, methyl or ethyl, CHOH R denotes hydrogen, chlorine, methyl, 'methoxy, ethoxy, 20 CH 'benzyloxy, car'boxy, carbomethoxy, or carboethoxy,

R denotes hydrogen or one or more methyl, methoxy, 0 ethoxy, i-propoxy, benzyl radicals or together with the ll 0 phenyl ring denotes a naphthyl, carbazolyl or diphenylene oxide radical and l R denotes hydrogen, methyl, ethyl or allyloxymethyl CH;-k N)-CH=N N v CmCOO and I I 1 Gin-(1H R denotes hydrogen, methyl, ethyl or allyloxymethyl and An( denotes an anion. 12. A hydrazone dyestutf of the formula 8. Hydrazone dyestufi of the formula cm w 0 m GHQ-N rr-cm '7 4 H R22 in cm Coo CH=N-N@ All) H;CH;-OH A i I &HRu HI OH u 13. A hydrazone dyestutf of the formula 7 0H 40 Cm wherein R denotes hydrogen, methyl, ethyl, n-propyl, allyloxymethyl or .phenoxymethyl,

R denotes hydrogen, methyl, ethyl, n-propyl, allyloxy- N H,

methyl or phenoxymethyl, with at least one of the radi- Alb-CHy-OH A cals R or R being hydrogen, methyl or ethyl, R denotes hydrogen or one or more methyl, methoxy,

ethqxy, i-propoxy, benzyl radicals or togetherwith the I References C'ted phenyl ring denotes a naphthyl, carbazolylprfdiphehyl- 5 UN TE S TES PATENTS ene oxideradicaland 1- fl 13,331,831 7/1967 Raue et a1. 260-162 za denotes hydrogfin, yl P Y d- 3,345,355 10/1957 R 2 0.41 5

An denotes an anion. v

- 9. A hydrazone dyestutiof the formula, FOREIGN PATENTS 226,855 4/1973 Austria 260-.240 G 1,532,806 6/1968 France zen-240G JOHN D. RANDOLPH, Primary Examiner CH=NN 11, N 1 US. Cl. X.R. I H:

C H 8-3, 7, 12, 177 -R, 179, 180; 106-22, 23; 162162;

CHzOH mf CDH 260-154, 155, 157, 158, 164, 165 

